Dispersible adhesive granules

ABSTRACT

A process for treating foliage by retaining an active agent in contact with the foliage is provided that includes the application of a biologically active ingredient carrier granule. The granule includes a mineral component, a cellulosic component, and a binder flowing upon wetting intermixed with the mineral component and the cellulosic components. A biologically active ingredient is added to the granule to treat the foliage. The foliage in either a dry or pre-wetted state. The contact of the granule with water causes the granule to flow to form a coherent film bound by the binder on the foliage with the active agent retained in the film in contact with the foliage.

RELATED APPLICATIONS

This application is a non-provisional application that claims prioritybenefit of U.S. Provisional Application 61/265,063 filed Nov. 30, 2009;the contents of which are hereby incorporated by reference.

FIELD OF THE INVENTION

The present invention in general relates to a biologically activeingredient granule and in particular to a biologically active ingredientgranule that is adherent to desired plant species.

FIELD OF THE INVENTION

The present invention in general relates to a biologically activeingredient granule and in particular to a biologically active ingredientgranule that is adherent to desired plant species.

BACKGROUND OF THE INVENTION

Biologically active ingredients are widely used in agriculture,landscape and turf management to kill or regulate the growth of desiredor unwanted plants, diseases, insects or other pests and/or to nourish,protect, regulate the growth, or enhance the appearance of desiredplants, and/or to modify the behavior of animals interacting withplants. In the course of a growing season, modern plant culture maydictate multiple treatments with biologically active ingredients. Apractitioner of plant culture must decide whether a particular treatmentis best performed with a granular product or a liquid spray application.Crops as diverse as turf, grain crops, tubers, ground fruits andvegetables, orchard crops, and horticultural plantings are routinelytreated with either granular or sprayed substances. Each applicationmethod has limitations. Specifically, while granular herbicide tends toprovide a simple broadcast, generally long-term release, accurateplacement of product in the treated area, relative freedom from spillsand other environmental releases, and safer handling, granules aredifficult to adhere to plant surfaces.

In contrast, spray treatment generally requires considerable skill forapplication, may contact only exposed foliage, and may tend todissipate, or “run off,” quickly. Spray treatment also has theundesirable attribute of spray drift that contaminates surrounding areaswith active agent intended for crop application. In spite of thedifficulties associated with liquid application, the improved adherenceproperties of liquid spray of biologically active materials targetingweed leaves or foliage make this a desirable route of delivery.

Regardless of whether spray or granule broadcast is used, theapplication method is not completely satisfactory. For instance, sprayapplication is quickly dissipated and leached into soil by rain.Granular formulations often require the use of additional herbicide dueto inefficiencies in the timely release, or inefficient environmentalextraction of the herbicide from the associated granular substratematerials.

Thus, there exists a need for a carrier granule carrying a biologicallyactive ingredient, the carrier adhering to the surface of plants,grasses and weeds using a granule that disperses rapidly when applied towetted foliage, dries quickly, and forms a film on a target that retainsa biologically active agent to the contacted foliage.

SUMMARY OF THE INVENTION

A process for treating foliage by retaining an active agent in contactwith the foliage is provided that includes the application of abiologically active ingredient carrier granule. The granule includes amineral component, a cellulosic component, and a binder flowing uponwetting intermixed with the mineral component and the cellulosiccomponents, A biologically active ingredient is added to the granule totreat the foliage. The foliage in either a dry or pre-wetted state. Thecontact of the granule with water causes the granule to flow to form acoherent film bound by the binder on the foliage with the active agentretained in the film in contact with the foliage.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A-D depict a progressive sequence of an inventive granule changewhen contacted with water.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention has utility as a granule to deliver a biologicallyactive ingredient to plant culture. Adherence of an inventive granule toa plant surface occurs with controlled granule size and density torestrict drift and promote retention on a target, along with water fromprecipitation, irrigation, dew, co-application with the granules fromspecial application equipment, or guttation water from the plant itself.An inventive granule, upon contact with a moistened plant surface orupon co-application with moisture, disperses on the plant surface tofacilitate the distribution and retention of the biologically activeingredient to the plant leaf and stalk.

An inventive granule retains its size and shape during handling andapplication to a desired area and adheres to moistened plant surfaceswhen the granule comes into contact with the plant. Thus, the durabilityof the particle affords both ease of application and adherence of thegranule on a desired site of action when sufficient moisture is presentto wet the granule surface, facilitating distribution and retention ofbiologically active ingredients to a target. Often without the presenceof added water from rain or irrigation, the moisture present on a plantsurface such as from ambient humidity or natural plant moisture is oftensufficient to activate the adherent properties of the inventive granule.

A granule is preferably sized such that it is applicable to a targetarea with minimal drift yet is not too large that the adherentproperties are thwarted by excessive size and density. As such, thesize, such as diameter, and density of an inventive granule are criticalfeatures of an inventive granule.

Typically, a granule has a diameter from 10 to 500 microns. Morepreferably, a granule has a diameter from 50 to 250 microns. In a mostpreferred embodiment, an inventive granule has a diameter of 100 to 150microns. Alternatively, 90% of the particles have a diameter less than150 microns.

An inventive granule includes a mineral component. Preferably, a mineralcomponent has greater density than a cellulosic component. In apreferred embodiment a mineral component has a density from about 0.8 to3 g/cm³. Suitable mineral components illustratively include rock dust,stones, clays, specific examples of which include limestone particulate,powdered dolomite, dolomitic limestone, gypsum, and pelletized lime. Amineral component is typically present in a granule according to thepresent invention in an amount from 10 to 90 total weight percent of thegranule.

An inventive granule further includes a cellulosic material with aparticle density less than the density of the mineral component. Theparticle density of the cellulosic component is preferably from about0.05 to 1 g/cm³. More preferably, a cellulosic component has a densityfrom about 0.08 to 0.6 g/cm³. Cellulosic materials operative hereinillustratively include grain hulls, peanut hulls, corncob, cereal, plantpulp, wood dust, and dried distillers grain (DDG), bait particulate, andother plant-based cellulosic materials. The cellulosic granule componentis readily formed through conventional techniques such as grinding andsieving, extrusion pelletization and sieving, and related techniqueswell known to the art. While it is appreciated that the cellulosicgranules operative herein are optionally formed by aggregating smallercellulosic fragments, in a preferred embodiment the cellulosic granulesare monolithic. Cellulosic granules are typically present in a granuleaccording to the present invention in an amount from 10 to 90 totalweight percent of the granule.

The inventive combination of mineral component of comparatively higherdensity and optionally larger mean particle size relative to cellulosiccomponent with a lower density and optionally smaller mean particle sizeprovides for a larger dispersion volume relative to mineral-basedgranular materials as detailed in U.S. Pat. No. 6,231,660 or 6,613,138,the contents of each are incorporated herein by reference. Morepreferably, the relative ratio of the mineral component and thecellulosic component promotes a particle with a density sufficient toresist drift during broadcast yet is not so heavy as to fail to adhereto a target due to gravitational and inertial forces during application.

In a preferred embodiment, the weight percent ratio of the mineralcomponent and the cellulosic component yield a granule with a densityfrom about 0.01 to 2 g/cm³. More preferably, the granule has a densityfrom about 0.05 to 1.5 g/cm³. In a most preferred embodiment theinventive granule has a density from about 0.08 to 1.2 g/cm³.

The inclusion of cellulosic component according to the present inventionallows product total density to be adjusted to facilitate bag filling.Additional advantages achieved through the inventive combination includeless mineral component fragmentation during transport and as a resultless product dusting during application. Still a further advantageincludes a larger volume of material to be applied by the end user so asto favor lower active agent dispersion density per area of vegetation soas to reduce overall active agent usage. It is appreciated thatconventional spreaders of granulated products provide limited end usercontrol over spreading density; adjustment of delivery medium accordingto the present invention is readily tailored to lessen over usage ofactive agents. A still further attribute of the inventive granule iswater absorption by cellulosic material that in turn facilitatesprolonged granule wetting and dispersion into a film on a target plant.

A binder component is preferably present in a granule in an amountranging from 0.1% to 75% by weight of the total dry weight of thegranule. A binder component is included in a particle as necessary toproduce or promote cohesion in forming a particle capable of retaining aspecified form during transport and/or distribution. A binder componentillustratively includes bentonite clay, carbohydrate, protein, lipid,synthetic polymer, glycolipid, glycoprotein, lipoprotein, lignin, alignin derivative, a carbohydrate-based composition, and a combinationthereof. In a preferred embodiment the binder component is a ligninderivative and is optionally calcium lignosulfonate. Alternatively, thebinder component is selected from the group consisting of: amonosaccharide, a disaccharide, an oligosaccharide, a polysaccharide andcombinations thereof. Specific carbohydrate binders illustrativelyinclude glucose, mannose, fructose, galactose, sucrose, lactose,maltose, xylose, arabinose, trehalose and mixtures thereof such as cornsyrup; celluloses such as carboxymethylcellulose, ethylcellulose,hydroxyethylcellulose, hydroxy-methylethylcellulose,hydroxyethylpropylcellulose, methylhydroxyethyl-cellulose,methylcellulose; starches such as amylose, seagel, starch acetates,starch hydroxyethyl ethers, ionic starches, long-chain alkyl starches,dextrins, amine starches, phosphates starches, and dialdehyde starches;plant starches such as corn starch and potato starch; othercarbohydrates such as pectin, amylopectin, xylan, glycogen, agar,alginic acid, phycocolloids, chitin, gum arabic, guar gum, gum karaya,gum tragacanth and locust bean gum; vegetable oils such as corn,soybean, peanut, canola, olive and cotton seed; complex organicsubstances such as lignin and nitrolignin; derivatives of lignin such aslignosulfonate salts illustratively including calcium lignosulfonate andsodium lignosulfonate and complex carbohydrate-based compositionscontaining organic and inorganic ingredients such as molasses. Suitableprotein binders illustratively include soy extract, zein, protamine,collagen, and casein. Binders operative herein also include syntheticorganic polymers capable of promoting or producing cohesion of particlecomponents and such binders illustratively include ethylene oxidepolymers, polyacrylamides, polyacrylates, polyvinyl pyrrolidone,polyethylene glycol, polyvinyl alcohol, polyvinylmethyl ether, polyvinylacrylates, polylactic acid, and latex. In a preferred embodiment, thebinder is calcium lignosulfonate, molasses, a liquid corn starch, aliquid corn syrup or a combination thereof.

Upon forming either of the mineral component or the cellulosiccomponent, a formulation of an active agent is applied to the granules.It is appreciated that one can: apply one or more liquid active agentsto the mineral component and separately apply one or more liquid activeagents to the cellulosic component, or alternatively, mix the mineralcomponent and the cellulosic component in a predetermined ratio with thebinder and thereafter apply one or more active agents to the intermixedcomponents or finished granules. Preferably, the active agent isdissolved in a solvent and applied to the preformed mineral component,cellulosic component, or a combination thereof. Alternatively, it isappreciated that a liquid active agent formulation is incorporated intoa binder solution during the formation of a granule An active agent inpowder form is intermixed with mineral component and cellulosiccomponent to form the inventive delivery granule. The active agentgranules are preferably of a mean size less than 20 percent that of themean mineral component size. Without intending to be bound to aparticular theory, electrostatic forces are believed to be operative toretain active agent powder in contact with the components of aninventive granule.

An active agent powder is alternatively adhered to an inventive granulesurface through resort to a surface tackifier. The tackifier coatingmakes the surface sticky to adhere the powder distinct from the binderthat is encompassed largely within the aggregated granule core.Preferably, active agent powder is sized such that the powder graindiameter has a mean particle diameter of less than 10% that of themineral component mean size. More preferably, the active agent powderhas a mean diameter of less than 2% that of the mineral componentparticle diameter. Effectively, any conventional active agent powder isoperative within the present invention.

A plasticizer is optionally added during or after the formation of agranule. By virtue of the inclusion of impregnated plasticizer accordingto the invention, the resulting granules are well suited to readilyabsorb substantial and repeated impacts, shears, or compressions. Theplasticizer-containing granule tends to deform while maintaining itsintegrity, increasing the attritional forces the inventive granule canabsorb before reaching a point of catastrophic failure. The amount offragments or dust formed as a result of such mechanical attrition isalso reduced. A plasticizer, such as glycerol, when introduced, resultsin the plasticizer being absorbed into the interior of the granule andincorporated into the granule without resulting in agglomeration.

When the plasticizer is introduced as a post-formation granule coating,the plasticizer provides to reformulate a granule to increase mechanicalrobustness. It is noted that the process of converting mechanicallysensitive granules to mechanically robust granules does not diminishdesirable properties such as ease of production, handling, solubility,enzymatic stability, thermal stability, and resistance to water pickupduring storage in humid conditions.

Suitable plasticizers which are incorporated into the granule arenonvolatile solvents which reduce the brittleness and enhancedeformability of the granule. Typically plasticizers are low molecularweight organic compounds generally with molecular weights between 50 and1000. Examples include, but are not limited to, polyols (polyhydricalcohols), for example alcohols with many hydroxyl groups such asglycerol, glycerin, ethylene glycol, diethylene glycol, triethyleneglycol, propylene glycol, dipropylene glycol, polyethylene glycol; polarlow molecular weight organic compounds, such as urea, sugars, sugaralcohols, oxa diacids, diglycolic acids; and other linear carboxylicacids with at least one ether group, C₁-C₁₂ dialkyl phthalates. Otherplasticizers operative herein illustratively include ethanolacetamide;ethanolformamide; triethanolamines such as triethanolamine acetate;thiocyanates, such as sodium and ammonium thiocyanates. Most preferredas plasticizers are glycerol, triethylene glycol, propylene glycol,sorbitol, and polyethylene glycol having an average molecular weightbelow about 600. Generally, the ratio of plasticizer to polymer rangesfrom about 0.05 to about 5.0. The plasticizer is preferably present at alevel of about 0.05 to about 25% by weight of total dry weight of thegranule, preferably about 1 to 10% by weight of total dry weight of thegranule; and more preferably about 1.5 to about 5.0% by weight of totaldry weight of the granule. The exact level depends on factors such asplasticizer identity, granule size, and plasticizer tack.

In one embodiment, an inventive granule disperses by breaking up intogreater than 100 smaller pieces upon contact with water over a period oftime ranging from 1 second to 24 hours. Preferably, an inventive granuledisperses into 1,000 to 10,000 smaller pieces over a period of timeranging from 1 second to 12 hours. Even more preferably, a granuledisperses into 100 to 10,000 smaller pieces over a period of 30 secondsto 6 hours. Most preferably, an inventive granule disperses as describedover a period of 5 seconds to 5 minutes. The swelling and dispersion ofan inventive granule is depicted graphically in FIGS. 1A-1D asrenderings derived from video imagery. FIG. 1A depicts a dry granule(t=0 sec), while FIGS. 1B-1D depict swelling and dispersion at times of2, 4, and 6 seconds, respectively.

In a preferred embodiment, a granule becomes flowable upon contact withwater to form a coherent film on a target. A film is typically circularwhen a target is horizontal and substantially flat. Typically, a filmhas a diameter between 0.1 and 100 times the diameter of the inventivegranule prior to flattening and spread flowing. Preferably, a film has adiameter of 1 micron to 5 microns. It is appreciated that an inventivefilm is produced upon flow of the inventive granule that is elongate inshape such as formation of a film during gravitational movement of aninventive granule during dispersion or a film is an irregular shapedictated by the shape of the target upon which dispersion occurs and asthe result of gravitational, wind, or other forces. In a preferredembodiment a granule disperses in between 1 second to 24 hours. Morepreferably, dispersion occurs between 1 minute and 1 hour. Mostpreferably, dispersion occurs in less than one minute.

Without intending to be bound to a particular theory, an inventivegranule contains a binder that is suspendable or soluble in water andupon granule wetting, a granule binder softens carrying constituentmaterial and cellulosic particulate therewith. Dynamically, a granule onfoliage upon wetting flattens in height and is observed to spread in twodimensions on the foliage surface, the particular constituents and theactive agent being retained as a coherent film by a matrix of binder.

The ability of the inventive material to flow with water is generallymeasured in a water dispersibility test. The test involves placing about10 grams of the inventive granules into 100 ml of water at roomtemperature in a closed glass container. The container is then invertedand the time is observed until the material disperses. After everyminute, the container is inverted. The inventive granules have adispersibility time of generally less than 15 minutes with a period ofless than 5 minutes being preferred and a period of less than 2 minutesbeing most preferred. The inventive particle provides delivery systemactive agents illustratively including plant nutrients, pesticides,hormones, herbicides, micronutrients, fungicides and other activeingredients.

Water-dispersible polymers are optionally coated onto inventivegranules. Water-dispersible polymers optionally function to break up aninventive granule into fine particles of no greater than about 50microns at room temperature within about 10 minutes of moderateagitation in deionized water or a solution of less than about 5% of adetergent or nonionic surfactant. Moderate agitation is applied throughthe use of a stir bar at a speed in the range of 100 to 300 rpm. Thewater-dispersible polymer is at least suspendable in water andpreferably has a solubility of at least 1% by total solution weight,more preferably at least 5% in deionized water at room temperature.

The water-dispersible polymers optionally present in an inventivegranule preferably have a molecular weight of more than 1,500 and arewater soluble or at least water suspendable. The water-dispersiblepolymers illustratively include polyvinyl alcohols (PVA), polyethyleneglycols (PEG), polyethylene oxides (PEO), polyvinyl pyrrolidones (PVP),cellulose ethers, alginates, gelatin, modified starches and substitutedderivatives, hydrolysates and copolymers thereof. Most preferredpolymers are PVA, cellulose ethers, such as methyl cellulose andhydroxylpropyl cellulose, gelatin and modified starches, such ashydroxypropyl starch produced from cornstarch. Mostly preferred is PVA.The polymers are optionally utilized in a foamed morphology. If PVA isused, in a preferred embodiment the polymer has a level of hydrolysis inthe range of about 50 to 99%, at least about 80%, at least about 85%, atleast about 90%, and at least about 95%. The polymer may have an averagemolecular weight of about 4,000 to 250,000, preferably from 5,000 to200,000; also from 10,000 to 100,000. The polymer generally constitutesabout 0.05% to about 10% total weight of the granule.

The granule preferably incorporates a biologically active ingredient(BAI) therein or coated on the carrier particle surface. The BAI ispresent in an amount ranging from 0.05% to 50% by weight of the totaldry weight of the granule. The BAI incorporated with the granuleillustratively include herbicides, insecticides, fungicides, plantgrowth regulators, pest reproductive control agent, other pesticides,macro (or primary) plant nutrients, secondary plant nutrients,micronutrients, biostimulants, or protective/coloring agents used tocoat or alter the appearance of plant surfaces for agronomic oraesthetic purposes, as well as other protectant and enhancing materials.It is appreciated that proteinaceous and microbial active agents such asB. thuringiensis bacteria and proteins.

Herbicides, for purposes of this invention, include a wide array of,chemical and biological compositions which include materials in thefunctional, or mode of action categories of desiccants, defoliants,abscission agents, algaecides, moss control agents (silvicides), acetylcoenzyme A carboxylase inhibitors, acetolactate synthase enzymeinhibitors, synthetic auxins (action like indoleacetic acid), inhibitionof auxin transport, inhibitors of photosynthesis at photosystem II SiteA and others with different binding behavior, inhibition of DHP(dihydropteroate) synthase, inhibition of acetyl CoAcarboxylase(ACCase), inhibition of lipid synthesis (not ACCase inhibition),inhibitors of 5-enolpyruvylshikimate-3-phosphate (EPSP) synthase orEPSPS inhibitor, inhibition of 4-hydroxyphenyl-pyruvate-dioxygenase(4-HPPD) (bleaching), inhibitors of glutamine synthetase, inhibitors ofcarotenoid biosynthesis, inhibition of carotenoid biosynthesis at thephytoene desaturase step (PDS) (bleaching), inhibition of allditerpenes, inhibitors of protoporphyrinogen oxidase (PPO), inhibitorsof dihydropteroate (DHP) synthase step, inhibitors of indoleacetic acidaction, inhibitors of cell wall (cellulose) synthesis, Site A inhibitorsof cell wall synthesis, Site B photo system I-electron diverters,inhibition of photosynthesis at photosystem 11, inhibitors of mitosis,uncoupling membrane disruptors, inhibition of4-hydroxyphenyl-pyruvatedioxygenase (4-HPPD), enolpynivylshikimate3-phosphate synthase enzyme inhibitors, synthetic auxins, uncoupling(membrane disruption), inhibition of VLCFAs (inhibition of celldivision), inhibition of mitosis/microtubule organization, microtubuleassembly inhibition, and other, unknown mechanisms. Biological, orbiorational, herbicides with application to this invention fallgenerally into the categories of bacteria, fungi, viruses, and plants,including the spore and other reproductive forms thereof, extractsderived therefrom, and including naturally occurring and geneticallyengineered forms.

More particularly, herbicides commonly fall into one (or more, in thecase of mixtures) of the following chemical families: aryloxyphenoxypropionates, arylaminopropionic acid, arsenicals, cineole (such ascinmethylin), cyclohexanediones, sulfonylureas, imidazolinones,pyrimidinylthio-benzoate, triazolopyrimidine, dinitroanilines,pyridazine, phenoxys (or phenoxies), benzoic acids, carboxylic acids(such as DCPA, clopyralid, trichloroacetic acid, and flouroxypyr),quinoline carboxylic acid, semicarbazone, triazines, triazinones,uracils, pyridazinone, phenyl-carbamates, nitriles, benzothiadiazoles,organoarsenicals, phenyl-pyridazine, ureas and substituted ureas (suchas diuron, linuron, siduron, tebuthiuron, dymron, etc.), amide (such aspropanil and bromobutide), thiocarbamates, organophosphates (such asbensulide), pyrazolium (such as difenzoquat), phosphoric acid compounds(such as glufosinate-ammonium and glyphosate), triazole, pyridazinone,nicotinanilide, pyridinone (such as fluridone), isoxazolidinone,diphenylethers, N-phenylphthalimides, oxadiazole, triazolinone,chloroacetamides, oxyacetamides, carbamate (such as asulam),phthalamate, phthalamate semicarbazone, nitrile, N-phenylphthalimides,oxadiazole, triazolinone, acetamides, benzoylisoxazole, isoxazole,pyrazole, pyrazolium, triketone, and benzofuran, biological herbicidesincluding Puccinia canaliculata, Puccinai jacea, Xanthomonas campestris,Alternaria destruens, Colletotrichzun gloeosporioides, Denthyphionpapaveraceae, Pseudomonas syringae, including any varieties orsubspecies thereof. Examples of plant extract herbicides are corn glutenmeal and the allelopathic exudates of various plants.

For purpose of this invention, a pest reproductive control agentoperative herein includes a pheromone, molting signaling compound orsteroid that upon contact with the target pest decreases thereproductive capacity of the pest. A pest reproductive control agent ispreferred over a pesticide since a reproductive control agent isspecific to a species or narrower group of organisms, does notbioaccumulate, and is less detrimental to predatory or bystanderorganisms in the pest habitat. Additionally, a reproductive controlagent is unlikely to avoid the bait due to ill health effects associatedwith sampling, as is often the case with a lethal pesticide.

The pest reproductive control agent includes agents such as anacaracide, an antimicrobial, a bactericide, an entomopathogen, afungicide, a synthetic plant growth regulator such as a gibberlic acidsynthesis inhibitor or promoter, an herbicide, an insecticide, amolluscicide, a nemacide, a rodenticide, a pheromone, a chemosterilant,a viricide, an imagocide, a larvicide, an ovicide, a formicide, anaphidicide, a muscacide, a culicicide, an anophelicide, an arachnidcide,and a vespacide. Preferably, an inventive bait particle containing atoxic invertebrate pesticide also contains a mammalian and/or avianingestion repellant. More preferably, it also contains both mammalianand avian ingestion repellants to lessen the likelihood of incidentalingestion by bystander higher species. Mammalian ingestion repellantsillustratively include cadaverine, butyric acid, and capsaicin. Avianrepellants include artificial grape flavorant.

For purposes of this invention, plant and general disease control agentsinclude fungicides, fungistats, antibiotics and bacteriocides of thefollowing chemical families and functional groupings; variousacetamides, sterol inhibitors or demethylase inhibitors, dicarboximides(such as iprodione), phthalides, phthalmic acids, triadiazoles,isophthalates, triazines, triconazoles, strobilurins, benzimidazoles,benzithiazoles, dithiocarbamates, carboxamides, carboxides or anilides,chlorphenyls, indolecarboxylic acids, isoxazoles, imidazoles,oxazolinediones, guanidines, diguanidines, piperidines, pyridines,sulfenamides, sulfonamides, quinolines, cyanoimidazoles, pyrazoles,pyrrolecarbonitriles, spiroketalamines, thiazoles, various chemicalfamilies of oomycete (pythium) fungicides, nitriles, chlorinatedhydrocarbons, phenylpyrroles, polyoxins, pyridazinones, mycotoxins (e.g.penicillin) or other antibiotics (e.g. streptomycin, kasugamycin,blasticidin, polyoxins, validamycin, mildiomycin, and oxytetracyline),morpholines, other organic compounds such as piperalin, piperazinederivatives and tolylfluanid, bronopol, organic compound mixtures (e.g.Bacticin and harpin protein), organic acids such as cinnamic acid andits derivatives, bacteria such as Agrobacterium radiobacter, Bacillussubtilus, Erwinia carotovora, Pseudomonas flourescens and P. chlorophis,and any varieties or strains thereof, fungi such as Candida oleophila,Fusarium, Tricoderma, Streptomyces, and Ampelomyces and any species,varieties or strains thereof, and viruses such as Tomovax.

For purposes of this invention, insecticides and acaricides includefast- and slow-acting neurotoxins, insect growth regulators, crop oil,feeding suppressants and repellants, acetylcholinesterase inhibitors,gamma-aminobutyric acid (GABA)-gated chloride channel antagonists,GABA-gated chloride channel antagonists, sodium channel modulators,acetylcholine receptor agonists/antagonists, acetylcholine receptormodulators, chloride channel activators, juvenile hormone mimics,feeding disruptors, mite growth inhibitors, ovicides, reproductiveinhibitors, reproductive sterilants, microbial disruptors of insectmid-gut membranes, inhibitors of oxidative phosphorylation at the siteof dinitrophenol uncoupling (disrupt adenosine triphosphate (ATP)formation), uncouplers of oxidative phosphorylation (disrupt H protongradient formation), inhibitors of magnesium-stimulated ATPase, Ecdysoneagonist/disruptors (disrupts insect molting by antagonizing the insecthormone ecdysone), octopaminergic agonists, Site I and Site II electrontransport inhibitors, inhibitors of chitin biosynthesis type1—Homopteran, inhibitors of chitin biosynthesis type 2-Dipteran,desiccants, fumigants, carbamates, organophosphates, chlorinatedcyclodienes, polychlorocycloalkanes, phenylpyrazoles, diphenylethanes,synthetic pyrethroids, pyrethrins, chloronicotines, (nitroguanidines),nicotine, Cartap, Bensultap, Spinosyns, Avermectin, Milbemycin, juvenilehormone analogues, Bt microbials (biological insecticide/larvicide),organotin matricides, pyrrole compound, sulfite ester matricides,substituted benzoylurea, thiadiazine, triazine, benzoic acid hydrazide,botanicals (neem oil or azadirachtin, rotenone), triazapentadiene,pyridazinone, and fatty acid soaps.

For purposes of this invention, plant growth regulators are ingredientssuch as trinexepac-ethyl, gibberellic acid, gibberellins, cytokinins,benzyladenine, glycines, quinolenes, phosphoric acid compounds, organiccarbamates, quaternary ammonium compounds, acetamides, ethychlozate,azoles, paclobutrazol, anilides, pyradazidine, pyrimidines,napthaleneacetamide, phthalmides, phenoxies, pyrimidines, hybridizingagent, biostimulants, seaweed extracts and herbicides (typically at lowuse rates), phthalmides, phenoxies, organic or carboxylic acids (e.g.gamma amino butyric acid and L-glutamic acid, napthalene acetic acid,clofencoet, sintofen, nicotinic acids), and herbicides (typically at lowuse rates).

For purposes of this invention, other pesticides include animal and birdrepellants, bitter flavors, irritants, and malodorous ingredients,molluscicides (e.g., slugs and snails), nematicides, rodenticides,defoliants, chemosterilants, plant defense boosters (harpin protein andchitosan) desiccants (may also be used as a harvest aid), and otherbeneficial or detrimental agents applied to plant or other surfaces.

For purposes of this invention, other protectants and beneficialingredients include attractants, baits, herbicide safeners,antidessicants, antitranspirants, frost prevention aids, inoculants,dyes, brighteners, markers, synergists, pigments, UV protectants,antioxidants, leaf polish, pigmentation stimulants and inhibitors,surfactants, moisture retention aids, humic acids and humates, ligninsand lignates, molluscicides (e.g., slugs and snails), nematicides,rodenticides, defoliants, desiccants, sticky traps, and IPM lures.

Optionally, the granule incorporates a fertilizer, soil nutrient,amendment material, or other active agent such as a biologically activeingredient (BAI), fungicide, pesticide or the like. In a granuleincorporating a fertilizer, soil nutrient or amendment material, thefertilizer, soil nutrient or amendment material is present in an amountranging from 0.05% to 50% by weight of the total dry weight of thegranule. In a more preferred embodiment, the fertilizer, soil nutrientor amendment material active ingredient is present in an amount rangingfrom 0.1% to 30% by weight of the total dry weight of the granule. In astill more preferred embodiment, the fertilizer, soil nutrient oramendment material active ingredient is present in an amount rangingfrom 0.5% to 10% by weight of the total dry weight of the granule.

Fertilizers are substances containing one of the plant nutrientsnitrogen, phosphate or potassium and illustratively include urea,sulfur-coated urea, isobutylidene diurea, ammonium nitrate, ammoniumsulfate, ammonium phosphate, triple super phosphate, phosphoric acid,potassium sulfate, potassium nitrate, potassium metaphosphate, potassiumchloride, dipotassium carbonate, potassium oxide and a combination ofthese. Soil nutrients illustratively include calcium, magnesium, sulfur,iron, manganese, copper, zinc; oxides thereof, salts thereof andcombinations thereof. Amendment materials are natural organic productssuch as humic acid, blood meal, bone meal, seed meal, feather meal andsoy meal; meat meal; animal waste from various animal sources; activatedsludge, hydrolyzed animal hair; fish byproducts; chitin; composts; and acombination thereof.

An inventive granule is produced by a number of processes. In oneparticular instance of the present invention, granule componentsincluding carrier particles, biologically active ingredients, andoptionally plasticizers, are wet granulated through a process of steps,including mixing of various dry components, wet massing the dry powdermixture with liquid surfactants, binders or the like, alone or with theaddition of a solvent to arrive at a suitable consistency forgranulating. Resulting powder mixture is compressed into a large formthat is subsequently ground to a desired size. It is appreciated thatdry granulation is facilitated by the addition of a pressing agent, suchas a stearate salt. Upon forming a granule, a granule is optionallycoated with water-dispersible polymers.

Alternatively, an inventive granule is made through a layering coatingprocess on carrier particles. A carrier particle is optionally formedfrom a mineral component, a cellulosic component, or a combinationthereof. Upon forming a carrier particle, a liquefied formulation of abiologically active ingredient (BAI) is applied to a carrier particlesurface. Preferably, the biologically active ingredient (BAI) isdissolved in a solvent. Alternatively, it is appreciated that the liquidbiological guttationly active ingredient (BAI) formulation isincorporated into a binder solution that promotes cohesion in theforming of the carrier particle with the proviso that the resultingcarrier particle surface has sufficient tack to adheremoisture-activated coating powder to the surface of the resultingcarrier particle.

A moisture-active coating illustratively includes gum arabic, guar gum,gum karaya, gum tragacanth, and locust bean gum. The moisture-activecoating constitutes in an amount of 0.5% to 10% by weight of the totaldry weight of an inventive granule. In one particular instance accordingto the present invention, water-dispersible polymers are combined to amoisture-active coating and the resulting mixture is sprayed ontoinventive granules.

It is appreciated that the present invention affords a more efficientusage of an active agent through initial broadcast adhesion to plantfoliage. Additionally, cutting of foliage so treated and allowing theclippings to remain in contact with the treatment area provides a secondopportunity for adhered active agents to provide an intended action. Alesser quantity of active agent is thereby used to achieve a desiredresult relative to conventional active carriers and usage techniques.

EXAMPLES Example 1 Preparation of an Active Granule

Using a pan agglomeration disk, the following components are combinedand mixed: 2 kilograms of +100 and −40 mesh (0.15-0.42 mm) limestoneparticulate, 1.8 grams of clopyralid, 1.5 grams iprodione as apesticide, 80 grams of calcium lignosulfonate as a binder, 60 grams ofglycerol as a plasticizer. The agglomeration disk is operated andadjusted to generate carrier particles in a size ranging from 10 to 500microns before the particles are conveyed to a fluid bed dryer where theparticles are dried to contain less than 0.5% moisture by weight at atemperature of 140° Fahrenheit. The particles are then separated intovarious size categories using conventional gyroscopic screeners. Carrierparticles with mean a size of 200 microns are fed to a blender (Forbergfluidized zone blender). The carrier particles are sprayed with a guargum solution. After coating with the guar gum solution, the resultinggranule contains guar gum of 5% by weight of the granules. It is notedthat application of granules of a particular size depends on the type ofplant leaf or stalk. Inventive granules have a size of 10 to 500 micronsare applied to pre-moistened turf at a broadcast density of clopyralidof 0.08 kg active ingredient per hectare. Greater than 95 number % ofthe granules are noted to adhere to the blade and stalk surfaces.

Example 2 Carrier Granules Preparation with Active Coating

The procedure of Example 1 is repeated with the exception that theiprodione is omitted. The resulting granules perform as detailed inExample 1.

Example 3

A limestone based dense mineral component formulation is preparedsubstantially according to Examples 1-7 of U.S. Pat. No. 6,231,660 toyield a dense mineral component having a density of 0.99 g/cm³ and anindex of uniformity of between 20 and 60. Forty parts by weight of theresultant dense mineral component are mixed with 60 parts per weight ofpeanut hull ground to a mean size guide of 75 microns and an index ofuniformity of between 20 and 60 to yield a mixture density of 0.57g/cm³. The resultant material is mixed with 0.1 parts by weight ofλ-cyhalothrin. The resulting material is packaged in 50 pound bags andtransported to an end use field where the material was spread with arotary spreader. As a comparative, 1 part of λ-cyhalothrin was combinedwith 100 parts by weight of only dense material containing granules andas a separate comparative with 100 parts by weight of only cellulosicgranules. The end user noted greater ease of spreading for the inventivecombination material as relative to the comparatives with an activedistribution per unit area of ground more closely aligned to target arealoadings relative to the comparatives. It was also noted that a largeportion of the granules disperse when contacted with rain, irrigation,or other moisture present on the target which has many benefits likeincreased efficacy and less risk of non-target pickup.

Example 4

The granule of Example 3 is reproduced with the replacement of thepeanut hull with extruded pelletized corncob of the same mean size anddistribution. Fifty parts by weight of the dense material containinggranules of Example 3 are mixed with 50 parts by weight of extrudedpelletized corncob to yield a material having a density of 600 g/cm³.The results for this delivery medium were comparable to those for theinventive medium of Example 3.

Patent documents and publications mentioned in the specification areindicative of the levels of those skilled in the art to which theinvention pertains. These documents and publications are incorporatedherein by reference to the same extent as if each individual document orpublication was specifically and individually incorporated herein byreference.

The foregoing description is illustrative of particular embodiments ofthe invention, but is not meant to be a limitation upon the practicethereof. The following claims, including all equivalents thereof, areintended to define the scope of the invention.

The invention claimed is:
 1. A process for treating foliage by retaining an active agent in contact with the foliage comprising: applying a biologically active ingredient carrier granule comprising: a mineral component; a cellulosic component; a binder flowing upon wetting intermixed with said mineral component and said cellulosic components; a water-dispersible polymer coating said granule, said coating breaking up said granule into fine particles upon wetting; and a biologically active ingredient; to the foliage in a dry or pre-wetted state; contacting said granule with water to cause said granule to flatten and flow to spread on the foliage surface to form a coherent film bound by said binder on the foliage with said active agent retained in said film in contact with the foliage.
 2. The process of claim 1 wherein the foliage is pre-wetted or wetted simultaneous with said applying of said granule.
 3. The process of claim 1 wherein the foliage is pre-wetted.
 4. The process of claim 1 further comprising: cutting the foliage to yield clippings; and placing the clippings within a target area in need of said active agent.
 5. The process of claim 1 wherein said granule disperses in less than 5 minutes.
 6. The process of claim 1 wherein said granule disperses in less than 1 hour.
 7. The process of claim 1 wherein said granule disperses upon contact with water in less than 6 hours.
 8. The process of claim 1 wherein the carrier granule has a diameter from 10 to 500 microns.
 9. The process of claim 1 wherein said mineral component is a material selected from tire group consisting of: limestone, dolomite, rock dust, and clay.
 10. The process of claim 1 wherein said cellulosic component is selected from the group comprising corncob, cereal, hulls, plant pulp, and wood flour.
 11. The process of claim 1 wherein said biologically active ingredient is selected from the group consisting of: herbicide, insecticide, fungicide, plant growth regulator, pest reproductive control agent, pesticide, and combinations thereof.
 12. The process of claim 1 wherein said carrier particle further comprises a plasticizer in an amount ranging from 1 to 10 total weight percent of said granule.
 13. The process of claim 12 wherein said plasticizer is selected from the group consisting of: polyols, urea, sugars, sugar alcohols, oxa diacids, diglycolic acids, linear carboxylic acids with at least one ether group, C|-C|₂ dialkyl phthalate, ethanolacetamide, ethanolformamide, tricthanolamines, thiocyanates, glycerol, rriethylene glycol, propylene glycol, sorbitol, and polyethylene glycol having an average molecular weight below about
 600. 14. The process of claim 1 wherein said granule further comprises a water-dispersible polymer selected from the group consisting of polyvinyl alcohol, polyethylene glycol, polyethylene oxide, polyvinyl pyrrolidone, cellulose ether, and hydroxypropyl starch.
 15. The process of claim 1 wherein said granule has a density of between 0.8 to 1.2 g/cm³ and a diameter of between 0.01 and 0.5 millimeters.
 16. The process of claim 1 wherein the foliage is blade grass.
 17. The process of claim 1 wherein the foliage is horticultural crop.
 18. The process of claim 1 wherein the foliage is an orchard crop. 